The present invention relates to new disazo dyes, a process for their preparation, their use for dyeing and printing polymeric materials, in particular cellulosic materials and leather, and liquid preparations containing these dyes and their use as recording liquids for ink jet recording apparatuses.
The new disazo dyes correspond to the formula (1) ##STR2##
wherein
R.sub.1 represents hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkyl-carbonylamino, ureido, or amino; PA1 R.sub.2 represents hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, sulfo, or carboxyl; PA1 R.sub.3 represents hydrogen; unsubstituted C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkyl substituted by NH.sub.2, di(C.sub.1 -C.sub.4 -alkyl)amino, OH, or C.sub.1 -C.sub.4 -alkoxy; unsubstituted aryl or aryl substituted one to four times in an identical or different manner by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, NH.sub.2, OH, sulfo, or carboxyl; ureido; formyl; C.sub.1 -C.sub.4 -alkylcarbonyl; or unsubstituted benzoyl or benzoyl substituted one to four times in an identical or different manner by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, sulfo, or carboxyl; PA1 R.sub.4 represents hydrogen, unsubstituted C.sub.1 -C.sub.4 -alkyl, or C.sub.1 -C.sub.4 -alkyl substituted by hydroxyl or C.sub.1 -C.sub.4 -alkoxy; PA1 the dotted lines represent an optional fused-on benzene ring; and PA1 n and n' independently of one another represent the number 0 or 1 with the provisos that PA1 R.sub.3, R.sub.4, n, and n' have the meanings stated above for formula (1) and the substituents are bonded to the naphthyl rings in the same positions as stated above for formula (1), and PA1 R.sub.5 represents hydrogen, C.sub.1 -C.sub.4 -alkyl, or C.sub.1 -C.sub.4 -alkoxy. PA1 R.sub.3, R.sub.4, n and n' have the meanings stated above for formula (1) and the bonding of the substituents in naphthyl ring A is in the same positions as stated for these substituents under formula (1), and PA1 R.sub.5 represents hydrogen, C.sub.1 -C.sub.4 -alkyl, or C.sub.1 -C.sub.4 -alkoxy. PA1 (1) 0.5 to 20% by weight of at least one dye of the formula (1), PA1 (2) 0 to 5% by weight (preferably 0.1 to 5% by weight) of at least one dye used for shading, PA1 (3) 50 to 99.5% by weight of water, PA1 (4) 0 to 30% by weight of one or more water-soluble organic solvents and/or agents having a hydrotropic action, and PA1 (5) 0 to 30% by weight of customary additives, such as agents which influence viscosity and/or surface tension, fungicides, bactericides and binders.
(i) in naphthyl ring A of formula (1) the OH group is in the 5-, 6-, or 8-position, the SO.sub.3 H group is in the 6-, 7-, or 8-position, the (SO.sub.3 H).sub.n group is in the 1-, 3-, or 4-position, and the azo group is in the 1- or 2-position, PA2 (ii) in naphthyl ring B of formula (1) the NR.sub.3 R.sub.4 group is in the 2- or 3-position and the (SO.sub.3 H).sub.n group is in the 1- or 2-position, and PA2 (iii) the disazo dyes exclude the dye of the formula (2) ##STR3##
Disazo dye (2) is described in Japanese patent specification jp 1,172,907 and is claimed for use in polarizing sheets:
The dyes of the formula (1) according to the invention can each be present both as the free acid or partly or completely in the form of their salts. The dyes are generally employed as salts, particularly as lithium, sodium, potassium, ammonium, mono-, di- or tris(C.sub.1 -C.sub.4 -alkyl)ammonium, mono, di or tris(C.sub.1 -C.sub.4 -alkanol)ammonium, or mixed (C.sub.1 -C.sub.4 -alkyl) (C.sub.1 -C.sub.4 -alkanol)ammonium salts.
The expression di(C.sub.1 -C.sub.4 -alkyl)amino in the definition of R.sub.3 denotes C.sub.1 -C.sub.4 -alkylamino and C.sub.1 -C.sub.4 -dialkylamino.
Preferred dyes of the formula (1) according to the invention are those which correspond to the formula (3) ##STR4##
wherein
Dyes that are particularly preferred because of their usually deep black desired shade have the formula (4) ##STR5##
wherein
The dyes (1) according to the invention can be obtained by a process in which aminonaphtholsulfonic acids of the formula (5) ##STR6##
(wherein the OH group is in position 5, 6, or 8, the SO.sub.3 H group is in position 6, 7, or 8, the (SO.sub.3 H).sub.n group is in position 1, 3, or 4, the amino group is in position 1 or 2, and n denotes the number 0 or 1) are diazotized and the resultant diazotization products are coupled to an aminobenzene or aminonaphthalene of the formula (6) ##STR7##
(wherein R.sub.1 and R.sub.2 and the dotted lines have the meanings stated above for formula (1)) and the aminoazo dyes formed in this reaction having the formula (7) ##STR8##
(wherein R.sub.1, R.sub.2, and n and the dotted lines have the meanings stated above under formula (1) and the bonding of the substituents in naphthyl ring A is as stated above for these substituents under formula (5)) are again diazotized and the resultant second diazotization products are coupled to aminonaphtholsulfonic acids of the formula (8) ##STR9##
(wherein R.sub.3, R.sub.4 and n' have the meanings stated under (1), the NR.sub.3 R.sub.4 group is in the 2- or 3-position, and the (SO.sub.3 H).sub.n' group is in 1- or 2-position).
Examples of suitable aminonaphtholsulfonic acids of the formula (5) include:
2-amino-5-naphthol-7-sulfonic acid, PA0 2-amino-5-naphthol-1,7-disulfonic acid, PA0 2-amino-8-naphthol-6-sulfonic acid, PA0 2-amino-8-naphthol-3,6-disulfonic acid, PA0 2-amino-6-naphthol-8-sulfonic acid, PA0 1-amino-5-naphthol-6-sulfonic acid, PA0 1-amino-5-naphthol-7-sulfonic acid, PA0 1-amino-6-naphthol-3,8-disulfonic acid, and PA0 1-amino-8-naphthol-4-sulfonic acid. PA0 1-amino-2- or -3-methoxybenzene, PA0 1-amino-2- or -3-methylbenzene, PA0 1-amino-3-ureidobenzene, PA0 1-amino-3-acetylaminobenzene, PA0 1-amino-2-methoxy-5-methylbenzene, PA0 1-amino-2,5-dimethylbenzene, PA0 1-amino-2,5-dimethoxybenzene, PA0 1-amino-2-methyl-5-acetylaminobenzene, PA0 1-amino-2- methoxy-5-acetylaminobenzene, PA0 1-amino-2-methyl-5-ureidobenzene, PA0 1-amino-2- methoxy-5-ureidobenzene, PA0 1-amino-5-acetylamino-2-sulfonic acid, PA0 1-aminonaphthalene-6- or -7-sulfonic acid, PA0 1-aminonaphthalene-6- or -7-carbonic acid, PA0 1-aminonaphthalene-2-methyl-6- or -7-sulfonic acid, and PA0 1-aminonaphthalene-2-methoxy-6- or -7-sulfonic acid.
Suitable aminobenzenes and aminonaphthalenes of the formula (6) include:
The following coupling components are examples of amino-naphtholsulfonic acids of the formula (8): 2-amino-, 2-methylamino-, 2-dimethylamino-, 2-(2-aminoethylamino)-, 2-(3-diethylaminopropyl-amino)-, 2-phenylamino-, 2-(4-sulfophenylamino)-, 2-(3-sulfophenyl-amino)-, 2-(4-carboxyphenylamino)-, 2-(3-carboxyphenylamino)-, 2-(4-methylphenylamino)-, 2-(2,4-dimethylphenylamino)-, 2-(4-methoxyphenyl-amino)-, 2-(4-aminophenylamino)-, 2-(4-amino-3-sulfophenylamino)-, 2-(4-benzoylamino-3-sulfophenylamino)-, 2-ureido, 2-acetamino-, 2-(N-ethyl-acetamino)-, 2-propionylamino-, 2-benzoylamino-, 2-(4-methylbenzoyl-amino)-5-hydroxynaphthalene-7-sulfonic acid; 2-amino-, 2-acetamino-, and 2-benzoylamino-5-hydroxynaphthalene-1,7-disulfonic acid; 2-amino-, 2-methylamino-, 2-dimethylamino-, 2-ethylamino-, 2-(2-hydroxyethyl-amino)-, 2-(bis-2-hydroxyethylamino)-2-(2-aminoethylamino)-, 2-(3-diethylaminopropylamino)-, 2-phenylamino-, 2-(4-sulfophenylamino)-, 2-(3-sulfophenylamino)-, 2-(4-carboxyphenylamino)-, 2-(3-carboxyphenyl-amino)-, 2-(2,4-dimethylphenylamino)-, 2-(4-methoxyphenylamino)-, 2-(4-aminophenylamino)-, 2-(4-amino-3-sulfophenylamino)-, 2-(4-benzoyl-amino-3-sulfophenylamino)-, 2-ureido, 2-acetamino-, 2-propionylamino-, 2-benzoylamino-, and 2-(4-methylbenzoylamino)-8-hydroxynaphthalene-6-sulfonic acid; and 2-amino-8-hydroxynaphthalene-6-sulfonic acid.
The diazotization of the aminonaphtholsulfonic acids of the formula (5) and of the aminoazo dyes of the formula (7) formed as intermediates is carried out in a known manner known, for example, with an alkali metal nitrite (such as sodium nitrite) in a mineral acid medium (preferably a hydrochloric acid medium) at temperatures of 0.degree. C. to 30.degree. C. (preferably 0.degree. C. to 15.degree. C.). The coupling of the diazotized aminonaphtholsulfonic acids of the formula (5) with an aminobenzene or aminonaphthalene of the formula (6) and the coupling of the diazotized aminoazo dyes of the formula (7) with an aminonaphtholsulfonic acid of the formula (8) are likewise carried out under customary known conditions. The coupling reaction is preferably carried out in an aqueous medium at a weakly acid, neutral, or alkaline pH and at temperatures of 0.degree. C. to 30.degree. C. (preferably 10.degree. C. to 25.degree. C.). A neutral to weakly acid pH (preferably in the range from 7 to 4) is advantageous for the coupling reaction with the aminobenzenes or aminonaphthalenes of the formula (6) and a neutral to weakly alkaline pH (preferably in the range from 7.5 to 9) is advantageous for the coupling reaction with the amino-naphtholsulfonic acids of the formula (8). The desired pH can be established and maintained by addition of bases, such as alkali metal hydroxides, carbonates, or acetates (for example, lithium, sodium, or potassium hydroxide, carbonate, or acetate), ammonia, or organic amines (for example, diethanolamine, triethanolamine, methyldiethanolamine, ethyidiethanolamine, dimethylethanolamine, or diethylethanolamine), or polyglycolamines (for example, the reaction product of ammonia with 6 mol of ethylene oxide).
The dyes according to the invention prepared in this way can be isolated by salting out with alkali metal salts, spray drying, or evaporation on a roll and then processed to water-soluble preparations with the customary standardizing agents and auxiliaries. The dyes can also be worked up to aqueous concentrated and stable solutions, with and without prior isolation, by subjecting their aqueous solutions or suspensions to a membrane separation process (particularly ultrafiltration), thereby largely freeing them from electrolytes and low molecular weight by-products. The liquid dye preparations are preferably free from organic solubilizing agents and generally contain 10 to 40% by weight (preferably 20 to 30% by weight) of at least one dye of the formula (1) according to the invention.
The invention also relates to the use of the disazo dyes of the formula (1) for dyeing and printing polymeric materials, particularly materials that contain carboxamide groups and/or are cellulosic, such as leather, cotton, regenerated cellulose fibers, and paper.
With respect to their properties, the dyes of formula (1) can be regarded as substantive or direct dyes and can therefore be used by all processes customary for substantive dyes in the leather, textile, and paper industry.
The dyes (1) are particularly suitable for the preparation of papers dyed in the pulp and on the surface. Thus, sized and non-sized grades of paper that can originate from bleached and non-bleached cellulose of various origins, such as softwood or hardwood sulfite or sulfate cellulose, are possible. For dyeing paper in the pulp, the dyes (1) are added to the paper pulp before the sheet formation. This addition can take place either in the thick matter after beating of the cellulose or in the thin matter before delivery to the papermaking machine. For dyeing paper sized in the pulp, the dyes (1) are preferably added to the thin matter before the sizing agent and for dyeing paper on the surface they are preferably dissolved in a concentrated starch solution and applied to the paper in this form using a sizing press. The dyes (1) can also be employed for dip dyeing of paper.
The dyes of the formula (1) according to the invention give dark violet to black dyeings with good wet- and light-fastnesses on the above-mentioned materials. In dyeing on paper, the dyes are distinguished by a high absorption. The paper dyeings obtained here in a high coloristic yield have good bleaching properties, are insensitive to alum and largely insensitive to pH, and are resistant not only to water but also to milk, fruit juices, and alcoholic drinks.
The dyes of the formula (1) according to the invention are also suitable for the preparation of recording liquids for ink jet printing processes, for example, in combination with bubble jet or piezo printing systems.
To prepare the printing inks, which are also according to the invention, one or more dyes of the formula (1) in a low-salt form that is as pure as possible are dissolved in water, if appropriate with the addition of one or more water-soluble organic solvents, hydrotropic auxiliaries and further customary additives. An aqueous dye solution that has been previously purified and concentrated by membrane separation processes, such as, for example, microfiltration, ultrafiltration, nanofiltration, reverse osmosis, or combinations thereof, is preferably used for the preparation of printing inks according to the invention. The preferred method is ultra-filtration on membranes that are permeable to salts and compounds having a molecular weight of less than about 20,000 dalton.
Organic solvents and agents having a hydrotropic action that are suitable for the printing inks according to the invention include mono- and polyhydric alcohols and ethers and esters thereof, nitriles, carboxylic acid amides, cyclic amides, ureas, esters, sulfones, and sulfoxides. Particularly suitable solvents include methanol, ethanol, propanol, ethylene glycol and the monomethyl, -ethyl and -propylether thereof, 1,2-propylene glycol, 1-methoxy- and 1-ethoxy-2-propanol, diethylene glycol, diethylene glycol monomethyl and monoethyl ether, dipropylene glycol, triethylene glycol, 1,5-pentanediol, glycerol, 2-hydroxyethyl and 2-(2-hydroxyethoxy)ethyl acetate, 2-hydroxypropionitrile, formamide, dimethylformamide, pyrrolidone, N-methylpyrrolidone, 6-caprolactam, N-methyl-6-caprolactam, urea, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethyl-propyleneurea, butyrolactone, dimethylsulfoxide, dimethyl sulfone, sulfolane, and polyethylene glycols having a molecular weight of up to 500 dalton.
Suitable additives that are customarily used in printing inks include both ionic and nonionic substances with which viscosity and/or surface tension can be established in the ranges required for use, as well as fungicides, bactericides, and binders (such as, for example, acrylate binders).
In addition to containing one or more dyes of the formula (1), the printing inks can also additionally contain other dyes known from the Colour Index that can be used for shading.
The printing inks according to the invention contain
Paper is the preferred recording material for ink jet printing systems.
The following examples further illustrate details for the preparation and use of the compounds of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these compounds. Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight.